JPH02298559A - Monoazo lake pigment and printing ink composition - Google Patents

Abstract

PURPOSE:To obtain a monoazo lake pigment useful for the coloring of printing ink by coupling a diazo component containing a specific benzolic amine compound with naphthol or naphthoic acid and converting the product to a lake. CONSTITUTION:The objective pigment is produced by coupling (A) a diazo component containing a benzolic amine having a soluble group and 0.1-20mol% (based on the whole diazo component) of a benzolic amine having a group of formula [R1 and R2 are H, 1-20C (un)saturated alkyl or (substituted) aryl] with (B) a coupler component composed of beta-naphthol or beta-oxynaphthoic acid and converting to a lake simultaneous to or after the coupling reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a monoazo lake pigment useful for various uses, particularly for coloring printing inks, and a printing ink composition using the same.

(Prior Art) Conventionally, monoazo lake pigments obtained from aromatic amines having soluble groups and β-naphthol or β-oxynaphthoic acid have been widely used for coloring printing inks, paints, plastics, etc., and in particular Pigment Red 57. (C,1
, 15850) is widely used as a pigment for process red inks. These monoazo lake pigments are treated with rosin at a ratio of 1 to 30% by weight in order to sharpen their color tone and improve their tinting strength, and the above-mentioned Pigmentlet 57 has a rosin treatment of 20 to 30% by weight based on the pigment content. % by weight of rosin is treated.

For example, when these pigments are used in printing inks.

With gravure ink, only high viscosity ink can be obtained.

In addition, the stability over time becomes poor, and in offset inks, rosin components are eluted in the dampening water, causing changes in fluidity when the offset ink is emulsified in water and a decrease in the surface tension of the ink emulsion water, reducing printability. There is a drawback.

In order to improve these drawbacks, studies have been made to synthesize rosin-less pigments or pigments in which the amount of rosin used is reduced to 1 to 7% by weight, but the hues are unclear and the tinting power is reduced.

(Problems to be Solved by the Invention) The present inventors have solved the above drawbacks by
The monoazo lake pigment obtained by using it as a monoazo lake pigment solves the above-mentioned drawbacks, has excellent sharpness and transparency, and has a greatly improved pigment composition that can be used as a pigment for printing inks and paints. I discovered that I can give things.

[Structure of the Invention] (Means for Solving the Problems) To explain the present invention in detail: 1. The aromatic amine as the diazo component used in the present invention is well known.

1 For example, l-amino-4-methylbenzene-2-sulfonic acid, 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid, 1-amino-4-methyl-5-chlorobenzene-2-sulfonic acid, Examples include 1-aminonaphthalene-2-sulfonic acid, 1-amino-4-chloro-5-methylhensen-2-sulfone M, and the like.

The coupler components are also known compounds such as β-naphthol,
Examples include β-oxynaphthoic acid and naphthol AS.

In the conventional method for producing an azo pigment using the above-mentioned raw materials, a zene-based amine is added to a diazo component and diazotized according to a conventional method. Then, the dye is mixed and coupled with the above-mentioned coupler component according to a conventional method, and the dye is made into a lake using a lake-forming agent, or the diazo component is mixed.

By adding a roughening lake agent to the coupler component and cambling, a monoazo lake pigment with improved suitability can be obtained according to the method of the present invention.

Of course, water-soluble resins and surfactants are included in the diazo component, coupler component, dye or pigment slurry.

Surface treatment of pigments by adding other additives = 3
- In the zene-based amine, one or two hydrogen atoms of the benzene nucleus are R, R of a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an ary group.
2 represents a group selected from a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, and an optionally substituted aryl group.

More specifically, 1, for example, 4-amino-benzenesulfonamide, 3-amino-4-methoxybenzenesulfonamide, 3-amino-4-methylbenzenesulfonamide, 3-amino-4-ethylbenzenesulfonamide,
3-amino-4-methoxy-N-butylbenzenesulfonamide, 3-aminobenzenesulfonamide, 3-amino-4-methylbenzenesulfonamide, 3-amino-4-methyl-N,N-dimethylbenzenesulfonamide, 3-amino-4-methoxy-N,N-diethylbenzenesulfonamide, 2-amino-N-ethyl-N-phenylhenzenesulfonamide, 3-amino-4-methoxy-N-eicozanhenzenesulfonamide.

4-Amino-N-dodecylbenzenesulfonamide.

3-Amino-N-octylhenzenesulfonamide.

3-amino-4-chlorohenzenesulfonamide.

3-amino-4-nitrobenzenesulfonamide and the like.

If it is less than 0.1 mol%, highly colored horns with great clarity, i
3.The effects of high brightness and good fluidity were not observed, and 20
Even if more than mol% is used, the effect of the amount used cannot be obtained.

Examples of the printing ink vehicle of the present invention include:

For off-cent inks, we use rosin-modified phenolic resin.

20 to 50 parts by weight of petroleum resins, alkyd resins, or drying oil-modified resins, O to 30 parts by weight of vegetable oils such as linseed oil, tung oil, soybean oil, n-paraffins, isoparaffins, aromatics, and naphthenes.

It consists of 10 to 60 parts by weight of a solvent such as α-olefin.

The monoazo lake pigment of the present invention is blended into this off-cent ink vehicle, and other ink solvents, dryers,
Known additives such as a leveling improver and a thickener are appropriately blended to prepare a printing ink composition.

In addition, gravure inks include gum rosin, wood rosin, tall oil rosin, mineralized rosin, lime rosin,
rosin ester, malein [=, gilt night,
Dammar, shellac, polyamide resin.

Vinyl resin, nitrocellulose, cyclized rubber monochloride rubber,
Ethyl cellulose, cellulose acetate, ethylene-vinyl acetate copolymer resin, urethane resin, polyester resin,
Resin mixture such as Alkit resin 10 to 50 weight 16Ln-
hexane, toluene, ethanol.

Methanol, acetone, ethyl acetate, ethyl lactate.

Cellosolve, diacetone alcohol, chlorhenzole, ethyl ether, acetal ethyl ether.

Solvents such as ethyl acetoacetate and butyl cellosolve acetate 30
~80 parts by weight 1 3 to 35 parts by weight of the monoazo lake pigment of the present invention, barium sulfate, barium carbonate, calcium carbonate,
It consists of 0 to 20 parts by weight of extender pigments such as slag, alumina white, clay, silica, silica white, talc, calcium silicate, precipitated magnesium carbonate, and other auxiliary agents such as a plasticizer and an ultraviolet inhibitor.

It contains an antioxidant, an antistatic agent, etc. as appropriate.

(Examples) The present invention will be explained below with reference to Examples. In the examples, 2 parts means parts by weight, and 1% means % by weight.

Example 1 1-amino-4-methylbenzene-2-sulfonic acid 17
．． 0 parts are stirred with 400 parts of water and 4 parts of sodium hydroxide at room temperature for 30 minutes to completely dissolve.

After acidifying by adding 25 parts of 35% hydrochloric acid, the following compound (
1) Add 2.5 parts and dissolve. Further, 58 parts of a 35% aqueous calcium chloride solution and 20 parts of ice are added and the mixture is cooled to 0°C to 3°C. Add 7 parts of sodium nitrite dissolved in 25 parts of water and continue stirring at 5°C or below for 30 minutes to obtain the diazo component.

On the other hand, 19 parts of β-oxynaphthoic acid was added to 1 part of natural rosin,
15°C with 1000 parts of water and 10 parts of sodium hydroxide
This is used as a coupler component. A coupler liquid is quickly mixed into the diazo liquid to complete the campling reaction and the lake formation reaction.

I) H of the coupling liquid is 10. . ~10. 'Met.

After heating to 80'C, the mixture was filtered, washed with water, dried and ground to obtain 45 parts of monoazo lake pigment.

The obtained pigment was made into an ink and tested as a pigment composition.

The pigment obtained above was made into an ink and tested. The varnish used was 50 parts of Tamanol 361 (Arayo Kagaku: rosin-modified phenolic resin), 20 parts of linseed oil, and 50 parts of linseed oil.
30 parts of No. Solvent (Nippon Oil Co., Ltd.: ink solvent) were added and melted by heating at 200°C. Then,
A gel varnish was prepared by adding 2 parts of aluminum octylate to 98 parts of this varnish.

70 parts of the obtained gel varnish, 20 parts of the red pigment of the present invention obtained using compound (1), and 10 parts of Solgent No. 1 (Nippon Oil Corporation: ink solvent) were blended.

The mixture was mixed and kneaded using three rolls to obtain an offset ink having a tank value of 9.0. The obtained Offsen 1-ink was significantly transparent and clear (as determined by visual inspection) and had excellent coloring power compared to Ink-8= obtained from a pigment to which compound (1) was not added. Note that 2. Coloring strength was determined by drawing down a mixture of 5. white ink and dark ink. The ink using the pigment of the present invention has coloring power, and the coloring strength is about 10% more than that of the ink using the comparative pigment.
I was able to add my own ink.

Example 2 1-amino-4-methylbenzene-2-sulfonic acid 17
．． 0 parts and 2.5 parts of the following compound (2) were added and diazotized according to a conventional method.

Separately, 19 parts of β-oxynaphthoic acid and 1 part of natural rosin are dissolved according to a conventional method to obtain a coupler liquid. The diazo component was added dropwise to the coupler component over a period of 30 minutes, and the mixture was stirred for an additional hour to complete the coupling reaction.

Next, 58 parts of a 35% calcium chloride aqueous solution was added and stirred for 2 hours to complete the lake formation reaction. After heating to 80°C, it was filtered, washed with water, and dried to obtain 45 parts of solid content.

The offset ink prepared from the obtained pigment was significantly transparent, clear, and had excellent coloring power compared to a conventional pigment that did not use the compound (2).

Example 3 1-amino-4-methylbenzene-2-sulfonic acid 16
．． 5 parts and 2-aminonaphthalene-1-sulfonic acid 0
．． After diazotizing 5 parts and the following compound (3) according to a conventional method,
A diazo component is obtained by adding 58 parts of a 35% calcium chloride aqueous solution. 19 parts of β-oxynaphthoic acid and 1 part of natural rosin
The coupler component is obtained by dissolving the parts. Mix both ingredients;
Complete the coupling reaction and lake formation reaction, and
After heating, the mixture was filtered and washed with water to obtain 45.5 parts of a monoazo lake pigment.

The off-cent ink prepared from this obtained pigment was compared to a conventional pigment that did not use compound (3).

,・ Author Ba transparent and clear 7 is 9th place 5 power 3-
Pile 7/Example 4 In place of compound (1) in Example 1, the following compound (
4) 44 parts of a monoazo lake pigment was obtained in the same manner as in Example 1 except that 2.5 parts were used.

The publication gravure ink prepared from this obtained pigment was compared with a conventional pigment that did not use compound (4).

It was extremely transparent, clear, and had excellent coloring power.

In addition, this test method involves filling a 200 cc mayonnaise bottle with the following composition.

Pigment: 1 part lime rosin varnish (20% solids, 75% toluene)
, plasticizer 5%) 90 parts diameter 3-fin glass peas 100 parts Paint conditioner was shaken for 2 hours to form a dark ink. Further, a light color ink was prepared by kneading 1 part of the dark color ink and 10 parts of the white ink, and the coloring strength was determined. The coloring power is the compound (4
) compared to ink prepared from pigments without added
It was a large percentage.

Example 5 1-amino-4-methylbenzene-2-sulfonic acid 17
．． 0 parts and 2 parts of the following compound (5) are added, diazotized according to a conventional method, and 58 parts of a 35% calcium chloride aqueous solution are added to obtain a diazo solution.

Separately, 19 parts of β-oxynaphthoic acid and 1 part of natural rosin were dissolved according to a conventional method to obtain a coupler liquid. The coupler liquid was rapidly mixed with the above diazo liquid to complete the campling reaction and the lake forming reaction, and after heating to 70°C, the mixture was filtered and washed with water to obtain 44 parts of solid content.

The off-cent ink prepared from the obtained pigment was significantly transparent, washable, and had excellent coloring power compared to a conventional pigment that did not use the following compound (5).

〔Effect of the invention〕

The monoazo lake pigment of the present invention has high tinting power, sharpness, and transparency compared to conventional ab pigments.

In addition to satisfying these effects, the fluidity is also good.

Further, when conventional azo pigments treated with a large amount of rosin have poor printability when used in printing inks, the azo pigments of the present invention have good printability.

The azo pigment of the present invention also has excellent thermal stability during flushing operations. That is, with conventional azo pigments, crystal growth and aggregation of pigment particles occurred during the heating operation during flushing, resulting in opacity of the ink and a significant decrease in coloring power.5 However, the azo pigment of the present invention does not have these drawbacks. It is a thermally stable pigment that does not generate any color.

Claims (1)

[Claims] 1. As a diazo component, there are benzene-based amines having a soluble group, and ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups (
However, R_1 and R_2 are hydrogen atoms, carbon atoms 1 to 20
represents a group selected from saturated or unsaturated alkyl groups and optionally substituted aryl groups. ), and there are the above ▲ mathematical formulas, chemical formulas, tables, etc. The benzene amines having the ▼ group contain a diazo component which is 0.1 to 20 mol% of the diazo component, and β-naphthol and β-oxynaphthoate. A monoazo lake pigment obtained by coupling a coupler component selected from acids and forming a lake at the same time or after the coupling. 2. A printing ink composition comprising the monoazo lake pigment according to claim 1 and a printing ink vehicle.